[go: up one dir, main page]

WO2013183919A1 - Matériau de cathode pour batterie secondaire ayant des caractéristiques de durée de vie améliorées et son procédé de préparation - Google Patents

Matériau de cathode pour batterie secondaire ayant des caractéristiques de durée de vie améliorées et son procédé de préparation Download PDF

Info

Publication number
WO2013183919A1
WO2013183919A1 PCT/KR2013/004931 KR2013004931W WO2013183919A1 WO 2013183919 A1 WO2013183919 A1 WO 2013183919A1 KR 2013004931 W KR2013004931 W KR 2013004931W WO 2013183919 A1 WO2013183919 A1 WO 2013183919A1
Authority
WO
WIPO (PCT)
Prior art keywords
lithium
oxide particles
transition metal
active material
cobalt oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2013/004931
Other languages
English (en)
Korean (ko)
Inventor
신선식
전혜림
이보람
박홍규
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LG Chem Ltd
Original Assignee
LG Chem Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to EP13801317.2A priority Critical patent/EP2835848B1/fr
Priority to CN201380023896.9A priority patent/CN104412424B/zh
Publication of WO2013183919A1 publication Critical patent/WO2013183919A1/fr
Priority to US14/533,528 priority patent/US10573880B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/003—Titanates
    • C01G23/005—Alkali titanates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Complex oxides containing manganese and at least one other metal element
    • C01G45/1221—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof
    • C01G45/125—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof of the type (MnO3)n-, e.g. CaMnO3
    • C01G45/1257—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof of the type (MnO3)n-, e.g. CaMnO3 containing lithium, e.g. Li2MnO3 or Li2(MxMn1-x)O3
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Complex oxides containing cobalt and at least one other metal element
    • C01G51/42—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2
    • C01G51/44—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2 containing manganese
    • C01G51/50—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2 containing manganese of the type (MnO2)n-, e.g. Li(CoxMn1-x)O2 or Li(MyCoxMn1-x-y)O2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention relates to a cathode active material and a manufacturing method for a secondary battery with improved lifespan characteristics.
  • Ni-MH secondary batteries are mainly used as power sources of such electric vehicles (EVs) and hybrid electric vehicles (HEVs).
  • EVs electric vehicles
  • HEVs hybrid electric vehicles
  • lithium secondary batteries of high energy density, high discharge voltage and output stability are used. Research is actively underway and some are commercialized.
  • lithium secondary batteries used in electric vehicles have high energy density and high power output in a short time, and must be able to be used for 10 years or more under severe conditions. Life characteristics are inevitably required.
  • Lithium ion secondary batteries used in conventional small cells generally use lithium cobalt oxide such as LiCoO 2 in a layered structure for the positive electrode and graphite-based materials for the negative electrode.
  • Lithium cobalt oxide is widely used because of its excellent physical properties such as superior cycle characteristics compared to LiNiO 2 and LiMn 2 O 4 , but cobalt (Co) is eluted in a high voltage or high temperature environment.
  • the present invention aims to solve the problems of the prior art as described above and the technical problems that have been requested from the past.
  • the present invention is to provide a cathode active material including lithium cobalt oxide particles with improved high voltage lifetime characteristics and a method of manufacturing the same.
  • the cathode active material according to the present invention for achieving the above object is characterized in that the lithium transition metal oxide particles containing lithium cobalt oxide particles and manganese (Mn) or titanium (Ti) coexist.
  • the lithium transition metal oxide particles containing manganese or titanium may be inserted into the lithium cobalt oxide particles or inserted into the grain boundaries of the lithium cobalt oxide particles.
  • the grain boundary means an interface between lithium cobalt oxide particles.
  • the positive electrode active material according to the present invention because the lithium transition metal oxide particles containing manganese or titanium coexist with the lithium cobalt oxide particles, without the phase change during high-rate charging and charging, manganese (Mn) or A compound composed of titanium (Ti) and lithium (Li) acts as a solid electrolyte, thereby exhibiting an effect of improving output characteristics.
  • the lithium transition metal oxide particles including Mn may be Li 2 MnO 3 .
  • Li 2 MnO 3 has a very good structural stability because a lithium-manganese mixed layer is present in the layered crystal structure and the manganese stable +4 is present as a cation.
  • the solid solution has a characteristic of showing a flat section in a high voltage section of 4.3V to 4.6V during charging, it is possible to improve the overall specific capacity of the positive electrode active material.
  • the lithium transition metal oxide particles including Ti may be Li 2 TiO 3 or Li 4 Ti 5 O 12 .
  • Li 4 Ti 5 O 12 has a structurally stable spinel structure and electrochemical activity, thereby improving the overall specific capacity of the positive electrode active material.
  • the average particle diameter of the lithium transition metal oxide containing manganese or titanium may be smaller or larger than the average particle diameter of the lithium cobalt oxide particles.
  • the lithium cobalt oxide particles may be particles having a particle diameter of 5 ⁇ m to 30 ⁇ m, and the transition metal oxide may have a structure having a particle size of 5 ⁇ m or less, and the final materials are LiCoO 2 and Li 2.
  • is MnO 3 (or Li 2 TiO 3, Li 4 Ti 5 O 12 , etc.) may be present separately, Li 2 MnO 3 into the interior of the LiCoO 2 is inserted (insertion) may possess only the shape of LiCoO 2.
  • the cathode active material may further include an electrochemically inert lithium compound on the outer surface of the lithium cobalt oxide particles, and the lithium compound may be specifically LiOH or Li 2 CO 3 .
  • lithium cobalt oxide contains a large amount of lithium impurities after firing in the manufacturing process, and these impurities adversely affect the manufacturing process of the secondary battery and the high temperature storage characteristics of the battery cell.
  • the positive electrode active material according to the present invention according to the manufacturing method described in detail below, in the positive electrode active material containing lithium cobalt oxide particles, the lithium impurities present with the lithium cobalt oxide particles, manganese or titanium By reacting with the containing compounds, the lithium transition metal oxide containing manganese or titanium is synthesized in lithium cobalt oxide, thereby improving the overall structural stability of the positive electrode active material.
  • the present invention provides a method for producing the positive electrode active material, specifically,
  • the mixing step may be a solid phase reaction or wet mixing.
  • the solid phase reaction is a method of mixing a solid lithium cobalt oxide and a solid transition metal providing compound, for example, a compound selected from the group consisting of MnO 2 , MnCO 3 , MnOOH, TiO 2 , TiCO 3 and TiOOH Can be.
  • the wet mixing is for example Mn (CH 3 COO) 3 , Mn (CH 3 COO) 2 MnSO 4 , Mn (NO 3 ) 2 , Ti (CH 3 COO) 3 , Ti (CH 3 COO) 2 TiSO 4 , Ti (NO 3 ) 2 of Water or alcohol
  • the method may be a method of dipping solid lithium cobalt oxide in a solution.
  • the mixing ratio of the compound containing lithium cobalt oxide and manganese or titanium in the step (a) can be determined according to the element molar ratio in the final product.
  • the present invention also provides a positive electrode mixture for a secondary battery including the positive electrode active material as described above, and a positive electrode for a secondary battery including the positive electrode mixture.
  • the cathode mixture may optionally include a conductive material, a binder, a filler, and the like.
  • the conductive material is typically added in an amount of 1 to 30 wt% based on the total weight of the mixture including the positive electrode active material.
  • a conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery.
  • graphite carbon black such as natural graphite or artificial graphite, acetylene black, Ketjen black, channel black, furnace black , Carbon black such as lamp black, summer black, conductive fiber such as carbon fiber, metal fiber, etc.
  • Metal powder such as carbon fluoride, aluminum, nickel powder, etc.
  • Conductive metal oxide polyphenylene derivative such as conductive whiskey titanium oxide such as zinc oxide and potassium titanate Conductive materials, such as these, can be used.
  • the binder is a component that assists in bonding the active material and the conductive agent to the current collector, and is generally added in an amount of 1 to 30 wt% based on the total weight of the mixture including the positive electrode active material.
  • binders include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene , Polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene butylene rubber, fluorine rubber, various copolymers and the like.
  • the filler is optionally used as a component that suppresses the expansion of the positive electrode, and is not particularly limited as long as it is a fibrous material without causing chemical change in the battery.
  • olefinic glass such as polyethylene or polypropylene may be used.
  • Fibrous materials such as fibers and carbon fibers are used.
  • the positive electrode according to the present invention may be prepared by applying a slurry prepared by mixing a positive electrode mixture including the above compounds in a solvent such as NMP onto a positive electrode current collector, followed by drying and rolling.
  • the positive electrode current collector is generally made to a thickness of 3 to 500 ⁇ m. Such a positive electrode current collector is not particularly limited as long as it has conductivity without causing chemical change in the battery.
  • the positive electrode current collector may be formed on a surface of stainless steel, aluminum, nickel, titanium, calcined carbon, or aluminum or stainless steel. The surface-treated with carbon, nickel, titanium, silver, etc. can be used.
  • the current collector may form fine irregularities on its surface to increase the adhesion of the positive electrode active material, and may be in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
  • the present invention also provides a lithium secondary battery composed of the positive electrode, the negative electrode, the separator, and a lithium salt-containing nonaqueous electrolyte.
  • the negative electrode is manufactured by applying a negative electrode mixture including a negative electrode active material on a negative electrode current collector and then drying the negative electrode mixture.
  • the negative electrode mixture may include components as described above, as necessary.
  • the negative electrode active material is, for example, carbon Li x Fe 2 O 3 (0 ⁇ x ⁇ 1), Li x WO 2 (0 ⁇ x ⁇ 1), Sn x Me 1 , such as non-graphitized carbon, graphite carbon -x Me ' y O z (Me: Mn, Fe, Pb, Ge; Me': Al, B, P, Si, Group 1, Group 2, Group 3 elements of the periodic table, halogen 0 ⁇ x ⁇ 1; 1 ⁇ y ⁇ 3; 1 ⁇ z ⁇ 8) such as metal composite oxide lithium metal lithium alloy silicon-based alloy tin-based alloys SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 3 O 4 , Sb 2 O 3 , Conductive polymer Li-Co-Ni-based materials such as metal oxide polyacetylene such as Sb 2 O 4 , Sb 2 O 5 , GeO, GeO 2 , Bi 2 O 3 , Bi 2 O 4 , and Bi
  • the negative electrode current collector is generally made to a thickness of 3 to 500 ⁇ m.
  • a negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery.
  • copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel Surface-treated with carbon, nickel, titanium, silver and the like on the surface, aluminum-cadmium alloy and the like can be used.
  • fine concavities and convexities may be formed on the surface to enhance the bonding strength of the negative electrode active material, and may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
  • the separator is interposed between the anode and the cathode, and an insulating thin film having high ion permeability and mechanical strength is used.
  • the pore diameter of the separator is generally from 0.01 to 10 ⁇ m ⁇ m, thickness is generally 5 ⁇ 300 ⁇ m.
  • a separator for example, a sheet, a nonwoven fabric, or the like made of olefin polymer glass fiber or polyethylene such as polypropylene having chemical resistance and hydrophobicity is used.
  • a solid electrolyte such as a polymer is used as the electrolyte
  • the solid electrolyte may also serve as a separator.
  • the lithium salt-containing non-aqueous electrolyte solution consists of an electrolyte solution and a lithium salt, and a non-aqueous organic solvent, an organic solid electrolyte, an inorganic solid electrolyte, and the like are used as the electrolyte solution.
  • non-aqueous organic solvent examples include N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, and gamma Butyl lactone, 1,2-dimethoxy ethane, tetrahydroxy franc, 2-methyl tetrahydrofuran, dimethyl sulfoxide, 1,3-dioxorone, formamide, dimethylformamide, dioxolon , Acetonitrile, nitromethane, methyl formate, methyl acetate, phosphate triester, trimethoxy methane, dioxorone derivatives, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbo Aprotic organic solvents such as nate derivatives, tetrahydrofuran derivatives, ethers, methyl pyroionate and ethyl propionate can be
  • organic solid electrolyte examples include polyethylene derivatives, polyethylene oxide derivatives, polypropylene oxide derivatives, phosphate ester polymers, polyedgetion lysine, polyester sulfides, polyvinyl alcohols, polyvinylidene fluorides, Polymerizers containing ionic dissociating groups and the like can be used.
  • Examples of the inorganic solid electrolyte include Li 3 N, LiI, Li 5 NI 2 , Li 3 N-LiI-LiOH, LiSiO 4 , LiSiO 4 -LiI-LiOH, Li 2 SiS 3 , Li 4 SiO 4 , Nitrides, halides, sulfates, and the like of Li, such as Li 4 SiO 4 —LiI-LiOH, Li 3 PO 4 —Li 2 S-SiS 2 , and the like, may be used.
  • the lithium salt is a good material to be dissolved in the non-aqueous electrolyte, for example, LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6, LiSbF 6, LiAlCl 4, CH 3 SO 3 Li, CF 3 SO 3 Li, (CF 3 SO 2) 2 NLi, chloroborane lithium, lower aliphatic carboxylic acid lithium, lithium tetraphenyl borate and imide have.
  • pyridine triethyl phosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphate triamide, nitro Benzene derivatives, sulfur, quinone imine dyes, N-substituted oxazolidinones, N, N-substituted imidazolidines, ethylene glycol dialkyl ethers, ammonium salts, pyrroles, 2-methoxy ethanol, aluminum trichloride and the like may be added. .
  • a halogen-containing solvent such as carbon tetrachloride or ethylene trifluoride may be further included, and carbon dioxide gas may be further included to improve high temperature storage characteristics, and FEC (Fluoro-Ethylene) may be further included.
  • carbonate), PRS (propene sultone), FPC (Fluoro-Propylene carbonate) may be further included.
  • the secondary battery according to the present invention may not only be used in a battery cell used as a power source for a small device, but also preferably used as a unit battery in a medium-large battery module including a plurality of battery cells.
  • the present invention provides a battery pack including the battery module as a power source of the medium and large devices, the medium and large device is an electric vehicle (EV), a hybrid electric vehicle (HEV), plug-in hybrid Electric vehicles and electric power storage devices including electric vehicles (Plug-in Hybrid Electric Vehicle, PHEV) and the like, but are not limited thereto.
  • EV electric vehicle
  • HEV hybrid electric vehicle
  • plug-in hybrid Electric vehicles and electric power storage devices including electric vehicles (Plug-in Hybrid Electric Vehicle, PHEV) and the like, but are not limited thereto.
  • FIG. 1 is a comparative graph of initial charge and discharge efficiency of a battery according to a non-limiting example of the present invention and a battery according to a comparative example;
  • FIGS. 2 and 3 are graphs comparing cycle characteristics of a battery according to a non-limiting example of the present invention and a battery according to a comparative example;
  • FIG. 4 is a graph comparing discharge capacity for each C-rate of a battery according to a non-limiting example of the present invention and a battery according to a comparative example.
  • the solid LiCoO 2 and the solid MnCO 3 were mixed, calcined at a temperature of 890 to 930 ° C. to produce LiCoO 2 treated with an Mn source, and then the Mn treated LiCoO 2 : conductive material: binder amount was 95: 2.5: After weighing to 2.5, and mixed in NMP to mix (mixing) to prepare a positive electrode mixture, the positive electrode mixture was coated with a thickness of 200 ⁇ m in 20 ⁇ m aluminum foil, and rolled and dried to prepare an electrode. The electrode was punched into a coin shape, and a coin-type battery was manufactured by using a carbonate electrolyte solution in which 1 mol of LiPF 6 was dissolved as a lithium metal and an electrolyte as a negative electrode.
  • the solid LiCoO 2 was immersed in an aqueous MnSO 4 solution and calcined at a temperature of 890 to 930 ° C. for 10 hours to prepare LiCoO 2 treated with an Mn source, followed by Mn-treated LiCoO 2 : conductive material: binder amount of 95: 2.5: 2.5 was weighed to 2.5 and put into NMP to mix (mixing) to prepare a positive electrode mixture, the positive electrode mixture was coated with a thickness of 200 ⁇ m in 20 ⁇ m aluminum foil and rolled and dried to prepare an electrode. The electrode was punched into a coin shape, and a coin-type battery was manufactured by using a carbonate electrolyte solution in which 1 mol of LiPF 6 was dissolved as a lithium metal and an electrolyte as a negative electrode.
  • a coin-type battery was manufactured in the same manner as in Example 1, except that the Mn source was not treated. (Bare LiCoO 2 )
  • the results are shown in Table 2, FIG. 2 and FIG. 3, in the case of the battery of Comparative Example 1, unlike the battery of Example 1 it was confirmed that the specific capacity is significantly reduced as the cycle is repeated.
  • the results are shown in Table 3 and FIG.
  • the positive electrode active material according to the present invention has a structure in which lithium transition metal oxide particles including manganese or titanium generated by reacting with lithium impurities in the positive electrode active material coexist with lithium cobalt oxide particles. It has the effect of improving the high voltage life characteristics and output characteristics.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

La présente invention concerne un matériau de cathode dans lequel des particules d'oxyde de cobalt-lithium et des particules d'oxyde de métal de transition-lithium contenant du manganèse ou du titane coexistent, et un procédé de préparation de celui-ci.
PCT/KR2013/004931 2012-06-04 2013-06-04 Matériau de cathode pour batterie secondaire ayant des caractéristiques de durée de vie améliorées et son procédé de préparation Ceased WO2013183919A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP13801317.2A EP2835848B1 (fr) 2012-06-04 2013-06-04 Matériau de cathode pour batterie secondaire ayant des caractéristiques de durée de vie améliorées et son procédé de préparation
CN201380023896.9A CN104412424B (zh) 2012-06-04 2013-06-04 具有增强的寿命特性的二次电池用正极活性材料及其制备方法
US14/533,528 US10573880B2 (en) 2012-06-04 2014-11-05 Cathode active material for secondary battery with enhanced lifespan characteristics and method of preparing the same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2012-0059526 2012-06-04
KR1020120059526A KR101836436B1 (ko) 2012-06-04 2012-06-04 수명특성이 향상된 이차전지용 양극 활물질 및 제조방법

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US14/533,528 Continuation US10573880B2 (en) 2012-06-04 2014-11-05 Cathode active material for secondary battery with enhanced lifespan characteristics and method of preparing the same

Publications (1)

Publication Number Publication Date
WO2013183919A1 true WO2013183919A1 (fr) 2013-12-12

Family

ID=49712263

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2013/004931 Ceased WO2013183919A1 (fr) 2012-06-04 2013-06-04 Matériau de cathode pour batterie secondaire ayant des caractéristiques de durée de vie améliorées et son procédé de préparation

Country Status (5)

Country Link
US (1) US10573880B2 (fr)
EP (1) EP2835848B1 (fr)
KR (1) KR101836436B1 (fr)
CN (1) CN104412424B (fr)
WO (1) WO2013183919A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102272265B1 (ko) 2014-11-21 2021-07-05 삼성에스디아이 주식회사 리튬 이차 전지용 양극 활물질, 이의 제조 방법 및 이를 포함하는 리튬 이차 전지
CN110546795A (zh) * 2017-04-27 2019-12-06 株式会社村田制作所 正极活性物质、正极、电池、电池包、电子设备、电动车辆、蓄电装置及电力系统
KR102270117B1 (ko) 2017-11-13 2021-06-28 주식회사 엘지에너지솔루션 리튬 코발트계 양극 활물질, 그 제조방법, 이를 포함하는 양극 및 이차 전지

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100693822B1 (ko) * 2003-06-23 2007-03-12 주식회사 엘지화학 표면 개질된 물질의 제조방법
JP2007280836A (ja) * 2006-04-10 2007-10-25 Sony Corp 非水電解質二次電池用負極合剤及び非水電解質二次電池
JP2011159639A (ja) * 2011-05-23 2011-08-18 Toyota Motor Corp 電極体及びその製造方法、並びに、リチウムイオン二次電池
JP2011228052A (ja) * 2010-04-16 2011-11-10 Toyota Industries Corp リチウムイオン二次電池
JP2012038539A (ja) * 2010-08-06 2012-02-23 Toyota Motor Corp 電池

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007108610A1 (fr) * 2006-03-20 2007-09-27 Lg Chem, Ltd. Oxyde de lithium-cobalt stoechiométrique et procédé de préparation associé
PL2005503T3 (pl) * 2006-03-20 2020-04-30 Lg Chem, Ltd. Materiały katody akumulatora litowego o wyższej wydajności
JP5077131B2 (ja) * 2007-08-02 2012-11-21 ソニー株式会社 正極活物質、並びにそれを用いた正極、および非水電解質二次電池
CN102769130A (zh) * 2007-09-04 2012-11-07 三菱化学株式会社 锂过渡金属类化合物粉末
KR20110025777A (ko) 2009-03-31 2011-03-11 파나소닉 주식회사 리튬 이온 전지용 양극의 제조방법, 리튬 이온 전지용 양극 및 상기 양극을 사용한 리튬 이온 전지
US9227850B2 (en) * 2009-10-05 2016-01-05 Nippon Chemical Industrial Co., Ltd. Positive electrode active material for lithium secondary battery, method for producing the same, and lithium secondary battery
JP2011134670A (ja) * 2009-12-25 2011-07-07 Toyota Motor Corp リチウム二次電池用正極活物質
JP5732351B2 (ja) * 2010-09-02 2015-06-10 日本化学工業株式会社 コバルト酸リチウムの製造方法
WO2012165020A1 (fr) * 2011-05-30 2012-12-06 日本電気株式会社 Matériau actif pour batteries secondaires, et batterie secondaire utilisant ledit matériau

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100693822B1 (ko) * 2003-06-23 2007-03-12 주식회사 엘지화학 표면 개질된 물질의 제조방법
JP2007280836A (ja) * 2006-04-10 2007-10-25 Sony Corp 非水電解質二次電池用負極合剤及び非水電解質二次電池
JP2011228052A (ja) * 2010-04-16 2011-11-10 Toyota Industries Corp リチウムイオン二次電池
JP2012038539A (ja) * 2010-08-06 2012-02-23 Toyota Motor Corp 電池
JP2011159639A (ja) * 2011-05-23 2011-08-18 Toyota Motor Corp 電極体及びその製造方法、並びに、リチウムイオン二次電池

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2835848A4 *

Also Published As

Publication number Publication date
EP2835848A4 (fr) 2015-09-16
KR101836436B1 (ko) 2018-03-08
US10573880B2 (en) 2020-02-25
EP2835848B1 (fr) 2018-09-19
EP2835848A1 (fr) 2015-02-11
KR20130136026A (ko) 2013-12-12
CN104412424A (zh) 2015-03-11
US20150056508A1 (en) 2015-02-26
CN104412424B (zh) 2020-06-19

Similar Documents

Publication Publication Date Title
EP3340348B1 (fr) Matériau actif d'électrode positive pour batterie secondaire au lithium, contenant de l'oxyde de cobalt et de lithium haute tension ayant un élément dopant, et son procédé de préparation
WO2015016563A1 (fr) Électrode comprenant une couche de revêtement pour empêcher une réaction avec l'électrolyte
WO2016099229A1 (fr) Matériau actif d'électrode positive mixte, électrode positive le comprenant, et batterie secondaire
WO2014073833A1 (fr) Matériau actif de cathode pour batterie secondaire et batterie secondaire qui comprend celui-ci
WO2015016548A1 (fr) Mélange de cathode pour batterie secondaire ayant un additif irréversible
WO2015016482A1 (fr) Procédé de pré-lithiation d'électrode anodique
WO2015026080A1 (fr) Matériau actif de cathode, batterie secondaire au lithium le comprenant et procédé de préparation de celui-ci
WO2013109038A1 (fr) Matière active de cathode, batterie rechargeable au lithium permettant de contrôler les impuretés ou le gonflement contenant celles-ci et procédé de préparation de matière active de cathode doté d'une productivité améliorée
WO2013137577A1 (fr) Précurseur pour la préparation d'oxyde de métal de transition au composite au lithium et procédé de préparation
WO2015016506A1 (fr) Matériau actif d'électrode à densité d'énergie améliorée et accumulateur au lithium le comprenant
WO2013009078A9 (fr) Batterie secondaire au lithium à haute énergie ayant des caractéristiques améliorées de densité d'énergie
WO2014010854A1 (fr) Matériau actif d'anode à haute tension et batterie secondaire au lithium comprenant celui-ci
WO2013157806A1 (fr) Procédé de fabrication d'électrode pour batterie rechargeable au lithium et électrode ainsi fabriquée
WO2013157832A1 (fr) Procédé de fabrication d'électrode pour pile rechargeable au lithium et électrode obtenue par ledit procédé
WO2015012640A1 (fr) Électrode pour accumulateur ayant une densité d'énergie améliorée et accumulateur au lithium la comprenant
WO2011084003A2 (fr) Matériau actif de cathode contenant un oxyde de lithium-manganèse qui présente d'excellentes caractéristiques de charge-décharge dans les régions 4 v et 3 v
WO2012039563A2 (fr) Matière active d'électrode positive comprenant de l'oxyde de manganèse et de lithium et batterie rechargeable à électrolyte non aqueux
WO2015012473A1 (fr) Oxyde à base de lithium et de manganèse et substance active d'électrode positive comprenant celui-ci
WO2011065650A2 (fr) Anode réalisée par une combinaison de deux éléments, et batterie secondaire au lithium l'utilisant
WO2011065651A9 (fr) Anode réalisée par une combinaison de deux éléments, et batterie secondaire au lithium l'utilisant
WO2015016531A1 (fr) Matériau d'anode actif pour batterie secondaire ayant une durée de vie améliorée
WO2015141997A1 (fr) Matériau actif d'électrode positive et batterie secondaire au lithium le comprenant
WO2013157811A1 (fr) Procédé de fabrication d'électrode pour batterie rechargeable au lithium et électrode ainsi fabriquée
WO2012039564A9 (fr) Matière active d'électrode positive à grande capacité dotée d'une conductivité améliorée et batterie rechargeable à électrolyte non aqueux comprenant celle-ci
WO2011122865A2 (fr) Matière active d'électrode positive et batterie rechargeable au lithium utilisant celle-ci

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13801317

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2013801317

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE